Dyeing or coloration of cellulose acetate



Patented Feb. 1 7, 193i j UNITE STATES PATENT OFFICE GEORGE-fiOLLAND ELLIS, or 'sronnon, NEAR DERBY, ENGLAND, ssIGNoR-ro CELANESE' CORPORATION ,or MERICA, A CORPORATION or DELAWARE i DYEING R COLORATION OF CELLULOSE ACETATE I m Drawing. Application fi led April s, 1926, Serial No. 100,178, and in }reat-Britain'1Iay 2, 1925.

' Thisinyention relates to the dyeing of colluloseacetate in theformof yarns, threads,

fabrics, films or other goods consisting of or containing 1t, by processes 1nvolv1ng the 0X1,-

5 dation of aniline, para-amino :phenol, para:

amino body or of a salt thereof, the oi zidation being eflected in a separatebath contalning persulphates, perborates and the like, or the phates, perborates-and the like. The presphenylenediamine, benzidine, tolidine, para amino diphenylamine, alpha-naphthylan ine,

or other amino .bodies on the fibre or' material, l

, It has been proposed to-dye cellulo'se'acetate by processes involvin the oxidation ofamino bodies on the fibre, the following meth- -1-. The ,fsingle bath? p h'cg's; in which t e; goods aretreated-in-a bath containing the amino base or salt thereof, togetherW1tl1 oXi-' dizing. agents e bichroniates. v

2..Th e two bath process, in which the goods arefirst soaked in .a;solutio'n ofthe oxidation being: eilectediin the exhausted base-bath after addition thereto of persulence in the baths of acids, salts and protective colloids has also bath process. v I p 3. The ageing process, in which the goods 39 are first treated with a solution of the amino bodyror, of a salt thereof, together with oxidizing agents and catalysts, the goods being dried after soaking, and thenheated in a warm atmosphere to effect or to complete oxidation. The presence in the impregnation bath of salts, acids and has also been proposed. Y

The dyeings produced on cellulose acetate by the oxidation .of amino bodies. on I the fibre by methods hitherto proposed have not been satisfactory, and in nearly all cases the processes cause loss of lustre of the fibreand yield dyeings loose to rubbing. In the single bath process aboye referred to there is usu-' ally vformation in the bath of insoluble coloring matter, which is adsorbed onthe surface of the goods, causing loss of lustre and looseness-to' rubbing. In the two bath process there is a great tendency during oxidation fortheamino body to be withdrawn from-the been proposed for, this tivo,

protective colloids ing soluble salts wi libre to the bath, and the dyeings produced suffer from the. same defects as those produced by the single bath process. In'the ageing process'a considerable amount of surface pigmentation of the goods results and the method yields dyeings loose tov rubbing, with loss of lustre of-the fibre.

acetate from aqueous solutions or dispersions so that-the fibre gradually absorbs the base' or bases in'the manner in which it absorbs dyestuffs from aqueous solutions or jdispersions;' and if then, preferably after rinsing, solutions or suitable oxidizing 'agent's',iwith or without-addition of catalysts ,or .offsalts,

or of both, are mechanically applied'by im I nation, and then, without rinsing, but

pre erablyafter drying, the goods are aged ,in an: atinosj)here of warm, moist'ai'r or of steam or air-and steam, oxidation proceeds exceedingly well, andthe results are free from the defect, of looseness't'o rubbing and loss of' llust're of the fibre.

According to the m ssiah the amino body or bodies are applied 'on the fibre or material from aqueous solutions v or dispersions, and

subsequently, preferably after rinsing, the" goods are impregnated with asolution or solutions of suitable oxidizing agents, contain- ,ingor-not containlng catalysts or salts, or

both catalysts and salts, and thereafter the goods, without rinsing, but preferably after drying, are subjected to ageing in an atmosphere of warm moist air, or of steam, or air and steam.

The amino body or bodies may be applied to the goods in any'suitable dilution, in form of their watersoluble salts, e. g. hydrochlorides.

Or the amino, body or bodies may be ap plied to the 'goods inlany suitable dilution, in form of their soluble or more? soluble modifications prepared by treating them. with sulphoricinoleic acid'or other sulphated ,fatty acids or other bodies of oily .or fatty characteristics, namely higher fatty acids or'sulphonated or other derivatives thereof containing salt forming roups capable of formti .alkalies or ammonia,

or with salts of such bodies,'such for instance as their alkali or ammonium salts; that is to say by treatin the amino body or bodies with the solubi lzingagents of the character referred to in British specification No. 219,349 and the corresponding U. S. Patent- No. 1,618,413. For simplicity, allof said solubilizing agents (including the salts) are hereinafter and in the claims included in the term body of oily or fatty characteristics. Corresponding to what is stated in the said specifications, the soluble or more soluble modifications ofthe amino body or bodies may be prepared by stirring up or treating the amino body or bodies with one or more of the said solubilizing agents, heating if necessary, and the mass can be afterwards diluted with water or aqueous alkali filtered if required, and added to. the dyebaths. .Solid solutions or concentratedpreparations of the amino body or bodies may be made by heating them with the body or bodies of oily or fatty character istics, for instance oleic, stearie, palmitic, or sulphoricinoleic acid, etc., (or their salts) either by treatment In presence of little or no water, or by treatment in presence of larger quatities of water with subsequent concentrationor dryin The solid solutions or concentrated solu ilized preparations may be diluted with hot water and added to the dyebath. 1

Or again, the amino body orbodies may be applied in the form of their soluble or-more, soluble modifications prepared by the methods described'in prior United States Patents Nos. 1,618,414 granted: February 22, 1927 1,690,481 granted November 6, 1928, and 1,694,413 granted December 11, 1928.

As stated in the said U. S. Patent No. 1,618,414 the method therein indicated consists in a pretreatment with one or more carbocyclic solubilizing agents, that is to say carbocyclic compounds containing in their structure one or more salt-forming groups or with sodium or other salts of said comagents the U. S. Patent acids,

pounds, or with mixtures of such carbocyclic 'solubilizing agents, or mixtures of one or referred .to in the said U. S. Patent No.1

1,618,414 may be effected similarly to the solubilization with aforesaid bodies of oily or fatty characteristics, and the solubilized forms or modifications may be similarly applied to-the goods.

1,694,413 consists in a pretreatment with solubilizing agents consisting of or comprising one or more Twitchell reagents, which term includes sulpho-aromatic fatty acids such as sulphobenzene stearic acid, sulphophenol stearic acid, or sulphonaphthalene stearic acid, and salts of sulpho-aromatic fatty acids. The solubilization. of-the amono body or bodies with the solubilizing' agents referred to in U. S. Patent No. 1,694,413 may be effected similarly to the solubilization with the aforesaid bodies of oily or fatty characteristics,.and the solubilized forms or modifications may be similarly applied to the goods.

The method indicated in U. S. Patent Iflo.

1,690,481 consists in a treatment comprising the employment, in conjunction with the aforesaid bodies of oily or'fatty characteris' tics, of auxiliary solvents, and the said U. S.

Patent No. 1,690,481 gives as examples of such auxiliary solvents alkyl or alkylene halides such for instance as tetrachlorethane, trichlorethylene; simple or mixed derivatives of the cyclic or aromatic series "containing one or more amino, chlor or hydroxy groups, such for example as cresols, alkylanilines,

toluidines, chlorphenols, monoor poly-chlor benzenes; hydrogenated derivatives of such or. other aromatic compounds, such for examfile as 'hexahydrophenol, hexahydrocresols, I

exahydrobenzene, tetrahydronaphthalene and the like. v Corresponding to what is stated in the said U. S. applicationSerial No. 48,666, which has issued as S. Patent No. 1,690,481 the amino body or bodies may be treated with one or more of the aforesaid bodies of oily or fatty characteristics and one or more of the auxiliary solvents,either in any order separately,

or together in admixture,-at anysuitable temperature or pressure, in presence or absence'of water, and the solubilized modifications so obtained may be added tothedyebaths. It will be understood that where the amino body or bodies are solubilized in accordance with themethod described in U. S.

application Serial No. 48,666 for the purpose 1 of practising the present invention, the auxiliary solvent or: solvents employed will be of a nature suitable to the process of the present invention, and thatin suchcases the use as auxiliary solvents of alkylanilines or other amino bodies or phenolic or naphthoic or other bodies which'would be absorbed substantively by the cellulose acetate and enter into oxidation reactions; would be avoided.

dekahydronaphthalene,

'The solutions or colloidal dispersions of the amino body or bodies may be applied to The method indicated in U. s. Patent No.

40 and the amino body or-bodies emfployed. 1 The tions containing the oxidizing agents may be performed in any suitable way, for instance in a padding or other mangle which gives a good squeeze out of excess liquor; or the goods, especially-hanks, may be wrung out on sticksby hand after dipping; the impregnation liquor is preferably applied to the -goodsin the cold.

A As oxidizingagents I may employ chlorates (such as sodium or potassium chlorates),

hypochlorites, bichroma-tes and the like, and catalysts .which I have found useful are salts of vanadium, iron. or copper, but any other suitable catalyst may be employed. a As "salts other than catalysts,

I may employ any suitable soluble salts, as for instance, Glauber salt, ammonium chloride, barium chloride,

calciuin chloride, magnesium chloride and.. v I I theli e. .Where acidsalts likely tovcause I v: L tendering ofthe'fibre arelus'ed,.acetatessuch 4 parts of alummmm d? Parts as calcium acetate or;sodium acetate, maybe added-to the impregnation liquor." As before mentioned the goods are. preferably. dried without rinsing after the impregnation.

The.ageing treatment in an atmospherev of-warm, mo st air, steam,.0ra1r and steam maybe carried out at any suitable tempera: ture and for any'suitable length of time, the treatment varyingv with the resultsdesired ageing treatment may be'per rmed in any suitable apparatus, as for instance in the continuous type of agein g machine which permits variable conditions of atmosphere,

or in the sim' le boxsteamer or ager.

After agein the goods-may berinsed, soaped, or 0t erwise treated to remove the metallic salts and finished-as desired. ,o

By the process of the present invention it is possible to obtain a great variety of shades according to the amino body, or bodies employed. By way of example the following shades may be obtained on acetyl cellulose When using the following amino bodies the process I I Aniline" -1; Grey or'blackf Para aminophenol l Fawn-brown.

Para aminodiphenylamine Black. Tolidine Green-black: Alphanaphthylamirie- Dull brown.

Paraphenylenediamine s Rich red-brown.

I .Itis to be understood that I do not limit myself to these examples, as a very great 2 parts of gum water, or very dilute for number of amino bodies may be used and a great variety of shades may-be obtained.

-The following are some examples of the manner in which the invention may be per formed, it being understood that these are mixed with 6 lbs, of 50% Turkey red oildiluted with soft water, and heated to 80 C. for a short while to effect solubilizationm dispersion. This is then diluted with hot Water and added through a. filter cloth to a dyebath containing 25 gallons, of soft water at C.- The goods are now .entered at this temperature and worked for two hours.

After rinsing well in soft water theyare im-.

pregnated' cold with their own weight of an oxidationsolution of the following 'compotragacarith dissolved in'300 I parts of water.

8 parts of chromium chloride 56 parts of I wateri of water.

dparts. of cupric chloride inparts V Add water to makeup to a total of 1000 parts.-

The goods are now aged (preferably after drying at a moderate temperature) ,"for 5 minutes in a steam ager, washed off in hot acid to remo-veimine ral matter. 'Dh a'rn lustre and handle being unimpaired. now be dried and finished as desired.

' Ewampl [I It may To dye 10 lbs.'of 'cellulose acetate in hank form amedium brown shade, lb. of benzi dine is solubilized or dispersed by warming 1 added through a-fi lter cloth to a dyebath containing 25 gallons of soft water. The goods are now entered, raised to 7075 C. in

hour and worked at this temperaturefor 1 hour; theyare now lifted and rinsed, and the base is oxidized by the impregnation and ci g gu process as detailed in the previous example. r"

After rinsing in dilute formic acid' 'th e goods will have acquired a dull brown shade,

1 cc. per litre) formic" :has now acquired adead black color'atiomf the lustre and handle being unimpaired. They treating as desired.

Example I I I To dye 10 lbs. of cellulose acetate in hank form afawn-brown shade, lb. of para aminophenol. is dissolved in 25 gallons of water, the goods are added, and the temperature is raised to T0-75 C. in hour, being maintained a further hour at this temperature. After lifting and rinsing, the base is oxidized as in Example I by the impregnation and ageing method. They will have acquired a fawn-brown color, lustre and handle bein unimpaired. After rinsing in 1 gram per itre of formic acid solution, the goods are now ready for drying or otherwise treating as desired.

Example I To dye 10 lbs. of cellulose acetate yarn in hank. form a deep brown shade, A; lb. of paraphenylenediamine is dissolved in sufficient water'a-nd added to a dyebath containing 25 gallons of water. The goods are entered, and the temperature is raised to 7075 C. in hour and maintained at this temperature for one hour. After rinsing, the goods are impregnated with a solution made up as follows 2 parts of gum tragacanth in 300 parts water. V 4 parts of aluminium chloride in 50 'parts of Water. r 3 partsof cupric chloride in 50 parts of water.

' 150 parts of sodium 'bichro'mate in 100parts y of water.

Makeup to 1000 parts with water. After squeezing evenly so that the fibre contains only its own weight of oxidizing mix- .ture, the goods are aged for 5 minutes in a to aging in a warm moist atmosphere.

2. Process for dyeing materials containing cellulose acetate, comprising applying to the materials at least one amino body from an aqueous colloidal solution, mechanically impregnating with a solution comprising an oxidizing agent and thereafter, without rinsing, subjecting to aging in a warm moist atmosphere.

3. Process are now ready for drying or otherwiseatmosphere.

for dyeing materials containing.

cellulose acetate, comprising applyin to the materials at least one amino body rom an aqueous colloidal solution prepared by pretreating the amino body with a solubilizing agent, mechanically impregnating with thereafter, without rinsing, subjecting to aging'in a Warm moist atmosphere.

4. Process for dyeing materials containing cellulose acetate, comprising applying to the materialsat least one amino body from an a'solution comprising an oxidizing agent and I aqueous colloidal solution prepared by pretreating the amino body with a solubilizing agent comprising a body of oily or fatty characteristics, mechanically impregnating with a solution comprising an oxidizing agent and thereafter, without rinsing, subjecting to aging in a Warm moist atmosphere.

5. Process for dyeing materials containing cellulose acetate, comprising applying to the materials at least one amino body from an aqueous solution, rinsing, mechanically impregnating with a solution comprising an oxidizing agent and thereafter, without rinsi o a n I ng, drylng and sub ecting to aging in a warm moist atmosphere.

6. Process for dyeing materials containing cellulose acetate,comprising applying to the materials at least one amino body with an aqueous colloidal solution,-rinsing, mechanically impregnating with a solution comprising an oxidizing agent and thereafter, without rinsing, drying and subjecting to aging in a wannmoist atmosphere.

7. Process for dyeing materials containing cellulose acetate, comprising a plying to the materials at least one amino.

with asolution comprising anoxidizing salt aging ina warm moist atmosphere.

. 8. Process for dyeing materials containing cellulose acetate, comprising applying to the materials at least one aminobody from an aqueousicolloidal solution, mechanically impre ating withf'a solution comprising an oxi izing salt and thereafter, without rinsing, subjecting to aging in a warm moist atmosphere. t

9. Process for dyeing materials containing cellulose acetate, comprising applying to the materials at least one amino body from an aqueous solution, mechanically impregnating with a solution comprising an oxidizing agent and a catalyst and thereafter, without rinsing, subjecting to aging in a warm moist 10. Process for dyeing materials containing cellulose acetate, comprising applying to .the materials at least one amino body from impregnatingwi'th a solution comprising an oxidizing agent and a catalyst and thereafter,

ody from an aqueous solution, mechanically impregnating without rinsing, subjecting to aging in a warm moist atmosphere.

25 an aqueous colloidal solution, mechanically agents, and thereafter,

11. Process for dyeing materials containing cellulose acetate, comprising applying to the materials at least one amino body from an aqueous solution, mechanically impregnating with a solution comprising an oxidizing agent and thereafter, withoutrinsing, subjecting to aging by steaming.

12. Process for dyeing materials containing cellulose acetate, comprising applying to the materials at least one amino body from an equeous colloidal solution, mechanically impregnating with a solution comprising an oxidizing agent and thereafter, without rinsing, subjecting to aging by steaming.

13. Process of dyeing materials containing cellulose acetate which comprises applying to such materials an aqueous solution of at least one amino compound, subjecting the thus treated material to the action of oxidizingv aging the said ma terial in a warm, moist atmosphere.

14.. Process of dyeing materials containing cellulose acetate which comprises applying to suchmaterials an aqueous solution of at least one amino compound prepared by pretreating the amino body with a solubilizing agent comprising a body of oily or fatty char- 'acteristics, mechanically impregnating the thus treated material with a solution containing a chlorate, and thereafter, Without rinsing, subjecting it to aging in a warm,'moist atmosphere.

15. Process of dyeing materials containing cellulose acetate which comprises applying to such materials an aqueous solution of at least one amino compound prepared by pretreating the amino body with a solubilizing agent,

rinsing, mechanically impregnating the thus treated material with a solution containing a chlorate, and thereafter, without rinsing, subjecting the material to aging in awarm, moist atmosphere.

16. Process of dyeing materials containing cellulose acetate which comprises applying to such materials an aqueous solution of at least pregnating the thus treated material with a solution containing a chlorate and a copper salt, and thereafter, without rinsing, drying, and subjecting it to "aging in a warm, moist I gum, chromium chloride, aluminum chloride,

cupric chloride and sodium chlorate,ldrying the material and then aging it in a damp, moist atmosphere.

In testimony whereof I have hereunto subscribed my name.

' GEORGE HOLLAND ELLIS.

one amino compound preparedby pretre'ating the amino body with a solubilizing agent, rinsing, mechanically impregnating the thus treated material with a solution containing a chlorate, and thereafter, without rinsing, drying, and subjecting the in a" warm, moist atmosphere.

' 17. Process ofdyeing materials containing cellulose acetate which comprises applying to such materials an aqueous solution of at least one amino compound, mechanically impregnating the thus treated material with a solution containing a chlorate and a catalyst,

and thereafter, without rinsing, drying, and subjecting it to aging in a mosphere.

18. Process of dyeing materialscontaining cellulose acetate which comprises. applying to such materials an aqueous solution of at least one amino compound, mechanically immaterial to aging warm, moist at- 

